US4309557A - Process for the preparation of alkyl and aryl substituted oligosiloxanes suitable for use as diffusion pump oils - Google Patents
Process for the preparation of alkyl and aryl substituted oligosiloxanes suitable for use as diffusion pump oils Download PDFInfo
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- US4309557A US4309557A US06/234,027 US23402781A US4309557A US 4309557 A US4309557 A US 4309557A US 23402781 A US23402781 A US 23402781A US 4309557 A US4309557 A US 4309557A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
Definitions
- the present invention is directed to an improved process for preparing alkyl and aryl substituted oligosiloxanes suitable for use as diffusion pump oils. More particularly, the present invention is directed to employing Grignard reactions for the preparation of 1,3,5-trimethyl, 1,1,3,5,5-pentaphenyltrisiloxane which is eminently suited for use as a diffusion pump oil.
- Organic liquids or oils have been in use for a long time as diffusion pump oils.
- an oil In order to be suitable for use as a diffusion pump oil, an oil must have low volatility and yet be vacuum distillable. Perhaps even more importantly, the oil must have a very high degree of thermal stability.
- 1,3,5-trimethyl,-1,1,3,5,5-pentaphenyltrisiloxane has hitherto been prepared by co-hydrolysis of the corresponding alkyl and aryl substituted chlorosilanes, by catalytic co-polymerization of tetraphenyldimethyldisiloxane and phenylmethylsiloxane, or by the reaction of the sodium salt of diphenylmethylsilanol with phenylmethyldichlorosilane.
- the principal object of the present invention was to provide an alternative synthetic route to alkyl and aryl substituted oligosiloxanes in general, and to 1,3,5-trimethyl,-1,1,3,5,5-pentaphenyltrisiloxane in particular.
- the desired synthetic route was expected to be more economical principally because of lesser degree of side product formation and hence better yields.
- the present invention utilizes aryl Grignard reagents to replace alkoxy leaving groups either in already formed alkyl, alkoxy substituted oligosiloxanes or in alkyl-alkoxy substituted silane precursors of the desired oligosiloxanes.
- aryl Grignard reagents to replace alkoxy leaving groups either in already formed alkyl, alkoxy substituted oligosiloxanes or in alkyl-alkoxy substituted silane precursors of the desired oligosiloxanes.
- an oligosiloxane or a silane containing alkyl and alkoxy substituents is reacted with an aryl Grignard reagent to provide, respectively, an oligosiloxane or silane having alkyl and aryl substituents.
- a compound having the general formula of Alkyl 1 --Si--(OAlkyl 2 ) 3 wherein Alkyl 1 has 1 or 2 carbons and Alkyl 2 has 1-6 carbons is allowed to undergo partial hydrolysis and condensation to provide the oligosiloxane having alkyl and alkoxy substituents.
- the oligosiloxane is then reacted with the aryl Gignard reagent to replace all of its remaining alkoxy substituents with aryl groups.
- the compound Alkyl 1 --Si--(OAlkyl 2 ) 3 is reacted with an aryl Gignard reagent in a manner so as not to replace all of the alkoxy substituents with the aryl group.
- the resulting alkyl-alkoxy-aryl-silanes are subjected to hydrolysis and substantially simultaneous condensation to give the desired alkyl-aryl-oligosiloxanes having no residual alkoxy groups.
- Trisiloxanes, and to a lesser extent disiloxanes, prepared in accordance with the present invention are useful as diffusion pump oils.
- the present invention is directed to the relatively economical preparation of compounds having the General Formula I which are useful as diffusion pump oils.
- n equals 0 to 1
- Alkyl 1 is an alkyl group having 1-2 carbons and R is an aryl or alkylaryl group, with the alklaryl group having 1 or 2 carbons in the alkyl chain.
- a diffusion pump oil must have low volatility and yet be distillable in high vacuum. It also must have a very high degree of thermal stability.
- the limitations regarding the number of siloxane moieties, and the nature of the alkyl and aryl or alkylaryl side chains in the compounds corresponding to General Formula I are principally imposed by the above stated requirements.
- the compounds of General Formula I are prepared by the use of a Grignard reagent which is characterized in General Formula V,
- X is Cl, Br or I and R is as defined as above for General Formula I.
- the Grignard reaction with the reagent R--Mg--X is preferably performed in tetrahydrofurane, although other solvents conventionally used for carrying out Grignard reactions may also be used. It was found desirable in some instances to add xylene or like high boiling inert solvent to the medium wherein the Grignard reaction is conducted in order to raise the reaction temperature.
- the Grignard reaction is performed on a compound having the General Formula VI in such a manner that not all of the alkoxy substituents of the compound are replaced by the R group of the Grignard reagent.
- Alkyl 1 is defined as above, and Alkyl 2 is an alkyl group having 1-6 carbons.
- both the desired monoaryl and diaryl substituted alkylalkoxysilanes are formed in the Grignard reaction, although usually some undesired triarylalkylsilane is also formed.
- the ratio of the several products in this Grignard reaction is influenced to some extent by the molar ratio of the Grignard reagent to the alkyltrialkoxysilane. For example when CH 3 --Si--(OCH 3 ) 3 is used, phenyl magnesium bromide is employed in a 1.5 to 1.75 molar ratio relative to CH 3 --Si--(OCH 3 ) 3 .
- the monoaryl and diaryl substituted alkyl-alkoxysilanes, the compounds of General Formulae VII and VIII, are usually separable from one another and from other contaminants by fractional distillation and/or fractional vacuum distillation. In some cases it is, however, advantageous to employ fractional distillation, and/or vacuum distillation merely to remove some of the more volatile monoaryl-alkylalkoxysilane (compound of General Formula VII), so as to adjust in the remaining mixture the molar ratio of the monoaryl-alkyl-dialkoxysilane (General Formula VII) to diaryl-alkylalkoxysilane (General Formula VIII) to approximately 1:2.
- methylphenyldimethoxysilane is formed in excess of its desired ratio. The excess is removed by distillation so that the remaining intermediate product mixture is adjusted to have an approximate ratio of methyl-phenyldimethoxysilane to methyl-diphenylmethoxysilane of 1.2:2.
- the removed excess of methyl-phenyldimethoxysilane may be added to the Grignard reaction wherein CH 3 --Si--(OCH 3 ) 3 is reacted with phenyl magnesium bromide to increase the yield of the desired methyl-diphenylmethoxysilane.
- the compounds of the General Formulae VII and VIII (present preferably in approximately 1:2 molar ratios) are heated with strong aqueous mineral base to affect hydrolysis of the remaining alkoxy groups. Substantially simultaneous condensation of the siloxane moieties yields a product mixture containing the desired compounds in accordance with General Formula I. Potassium hydroxide is well suited as the strong mineral base for affecting the hydrolysis and condensation.
- the product mixture of the hydrolysis and condensation reaction contains other components such as cyclic tri-, and higher siloxanes as well as linear tetra-, and higher siloxanes, the desired products may be readily isolated by fractional vacuum distillation.
- the cyclic and linear siloxane side products may be treated with strong mineral base such as KOH to cause equilibration and formation of more of the desired products corresponding to General Formula I.
- the alkyl-trialkoxysilane compounds of General Formula VI are partially hydrolyzed and simultaneously condensed to give intermediate alkyl-alkoxyoligosiloxanes, compounds corresponding to General Formula IX, wherein the symbols Alkyl 1 , Alkyl 2 and n have the same meaning as above. ##STR4##
- Products of the hydrolysis and condensation reaction include the desired intermediate di-, and trisiloxanes corresponding to the General Formula IX, as well as undesired cyclic tri-, and higher siloxanes, and linear tetra-, and higher siloxanes.
- the desired intermediate alkyl-alkoxydisiloxanes and alkyl-alkoxy-trisiloxanes may be respectively isolated in substantially pure states by distillation in vacuum. In practice however, it is sufficient to obtain a fraction which contains the desired alkyl-alkoxydisiloxanes and alkyl-alkoxytrisiloxanes substantially free of starting alkyl-trialkoxysilane and methanol.
- 1,3,3,5-tetraalkyl-1,1,5,5-tetraalkoxytrisiloxanes the compounds corresponding to General Formula X wherein Alkyl 1 and Alkyl 2 are defined as above, and Z is an alkyl group of 1-2carbons, are reacted with the Grignard reagent R--Mg--X to give, in excellent yields, 1,3,3,5-tetraalkyl-1,1,5,5-tetraaryltrisiloxanes.
- the letter compounds are represented by General Formula XI wherein Y has the same definition as Z above. ##STR5##
- 1,3,3,5-tetramethyl-1,1,5,5-tetraphenyltrisiloxane (Formula III) is obtained in this manner from 1,3,3,5-tetramethyl-1,1,5,5-tetramethoxytrisiloxane with the use of phenyl magnesium bromide.
- the starting material 1,3,3,5-tetramethyl-1,1,5,5 tetramethoxytrisiloxane may be obtained in accordance with the teachings of the prior art by reaction of dimethoxymethylsilanol with dimethyldicholorosilane.
- phenyl magnesium bromide as the Grignard reagent, methoxy group as the alkoxy substituents, and methyl group as the alkyl substituents is preferred in the several embodiments of the process of the present invention.
- CH 3 --Si--(OCH 3 ) 3 and H 2 O containing 1.25 g/l NaOH are continuously added to an agitated 5 L reaction vessel at a ratio of one mole CH 3 --Si--(OCH 3 ) 3 to 0.44 moles of H 2 O.
- the combined rate of addition of CH 3 --Si--(OCH 3 ) 3 and H 2 O is approximately 0.5 liters/minute.
- the reaction vessel is heated so as to maintain an internal temperature of approximately 65° C.
- the contents of the reaction vessel comprising the product of hydrolysis are allowed to exit by overflow into a storage container.
- the hydrolyzate is subjected to distillation to remove methanol and unreacted CH 3 --Si--(OCH 3 ) 3 (b.p 103° C. at 760 Hgmm) which is recovered in approximately 35% yield.
- the remainder of the hydrolyzate is subjected to vacuum distillation to isolate 1,1,3,5-tetramethoxy-1,3,-dimethyldisiloxane (b.p 44.5° C./3 mm) and 1,1,3,5,5-pentamethoxy-1,3,5-trimethyltrisiloxane (b.p 94° C./5 mm) either in respectively pure states or as a mixture with one another.
- the hydrolysis reaction also yields approximately 4 parts of the corresponding linear tetrasiloxane, and 2 parts of the corresponding linear pentasiloxane as well as other side products. Traces of sn, Pb and Fe ions interfere with the hydrolysis reaction. Therefore, special care must be taken to avoid these impurities.
- the reaction is best conducted in a glass vessel.
- Cooling of the reaction vessel, and if necessary, the rate of addition of bromobenzene, are adjusted so as to maintain an internal temperature between 65°-140° C.
- the addition of THF-xylene is discontinued when a total of approximately 155 kg of the mixture has been added.
- addition of 1,3,5-trimethyl-1,1,3,5,5-trimethoxytrisiloxane is commenced at a rate of 0.8 kg/min.
- a mixture of 1,3,5-trimethyl-1,1,3,5,5-trimethoxytrisiloxane and 1,3 -dimethyl-1,1,3,3-tetramethoxydisiloxane may be added at the same rate.
- a total of 19.0 kg of the above-noted trisiloxane or mixed trisiloxane and disiloxane are added in this manner.
- the addition of bromobenzene is continued until a total of 81.6 kg of bromobenzene has been added.
- heating is applied to the reaction vessel as necessary to maintain an internal temperature of approximately 94° C. for approximately 11/2 hours.
- cooling is applied and 33 kg of H 2 O is added.
- An aqueous (lower) and an organic (upper) phase separates.
- the organic phase contains THF, xylene and product.
- the THF, xylene and any residual bromobenzene are removed from the upper phase by strip distillation.
- the residue is subjected to fractional vacuum distillation to obtain 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane (b.p 245° C. at 0.5 Hgmm), and, if applicable, 1,3,-dimethyl-1,1,3,3-tetraphenyldisiloxane (b.p. 187° C. at approximately 0.5 Hgmm).
- the yield of the methylphenyl siloxanes is 95% or higher, based on the added methylmethoxy siloxanes.
- methyldiphenylmethoxysilane (b.p. 150° C. at 5 Hgmm) may be obtained in substantially pure states. These compounds are typically formed in approximately 1:1 ratio in the reaction. Alternatively and preferably, methylphenyldimethoxysilane is distilled out until the molar ratio of methyldiphenylmethoxysilane and methylphenyldimethoxysilane is adjusted in the residue to approximately 2.0:1.2. The concentration of these compounds is readily monitored by gas chromatography.
- a mixture of methyldiphenylmethoxysilane and methylphenyldimethoxysilane in the approximate molar ratio of 2.0:1.2 is refluxed with H 2 O and KOH for one hour. 10 moles of H 2 O and 0.08 moles of KOH are present for each 2 moles of methyldiphenylmethoxysilane. After reflux, the H 2 O and CH 3 OH which is formed in the reaction is distilled and trapped in a Dean-Stark-type trap, and the temperature is raised to 200° C. for one hour.
- 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane and 1,3-dimethyl-1,1,3,3-tetraphenyldisiloxane are obtained by fractional vacuum distillation.
- a typical reaction from 100 parts by weight of mixed methyldiphenylmethoxysilane and methylphenyldimethoxysilane 15 parts of 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane and 10 parts of 1,3,-dimethyl-1,1,3,3-tetraphenyldisiloxane are obtained.
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Abstract
Description
R--Mg--X GENERAL FORMULA V
Alkyl.sub.1 --Si--(OAlkyl.sub.2).sub.3 GENERAL FORMULA VI
Claims (56)
Alkyl.sub.1 --Si--(OAlkyl.sub.2).sub.3
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US06/234,027 US4309557A (en) | 1981-02-12 | 1981-02-12 | Process for the preparation of alkyl and aryl substituted oligosiloxanes suitable for use as diffusion pump oils |
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US06/234,027 US4309557A (en) | 1981-02-12 | 1981-02-12 | Process for the preparation of alkyl and aryl substituted oligosiloxanes suitable for use as diffusion pump oils |
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US4309557A true US4309557A (en) | 1982-01-05 |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4717773A (en) * | 1985-10-04 | 1988-01-05 | Kenney Malcolm E | Silicate esters and organosilicon compounds |
US4824985A (en) * | 1987-06-11 | 1989-04-25 | Dow Corning Corporation | Novel route to Ca8 Si4 O12 Cl8, alkoxycyclotetrasiloxanes, aryloxycyclotetrasiloxanes, alkylcyclotetrasiloxanes and arylcyclotetrasiloxanes from wollastonite (Ca SiO3) |
US5948539A (en) * | 1996-09-04 | 1999-09-07 | Medtronic, Inc. | Medical electrical lead and reinforced silicone elastomer compositions used therein |
US20030118761A1 (en) * | 2001-12-21 | 2003-06-26 | Kimberly-Clark Worldwide, Inc. | Elastomeric articles having improved chemical resistance |
US20040253459A1 (en) * | 2003-06-11 | 2004-12-16 | Kimberly-Clark Worldwide, Inc. | Composition for forming an elastomeric article |
US20050130522A1 (en) * | 2003-12-11 | 2005-06-16 | Kaiyuan Yang | Fiber reinforced elastomeric article |
US20050127578A1 (en) * | 2003-12-11 | 2005-06-16 | Triebes Thomas G. | Method of making fiber reinforced elastomeric articles |
US20060143767A1 (en) * | 2004-12-14 | 2006-07-06 | Kaiyuan Yang | Breathable protective articles |
CN104017017A (en) * | 2014-06-25 | 2014-09-03 | 四川科立鑫新材料有限公司 | Method for synthesizing phenyl-containing organosilicon monomers |
Citations (6)
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GB787800A (en) * | 1955-10-07 | 1957-12-18 | Midland Silicones Ltd | A novel trisiloxane |
GB808613A (en) * | 1957-01-03 | 1959-02-04 | Midland Silicones Ltd | Trisiloxane |
US3334318A (en) * | 1964-12-05 | 1967-08-01 | Mitsubishi Electric Corp | Stripline circulator having means causing electrostatic capacitance between adjacent pairs of terminals to be substantially equal to each other |
US3354101A (en) * | 1964-12-29 | 1967-11-21 | Union Carbide Corp | Preparation of organosilicon compounds |
US3523131A (en) * | 1968-10-15 | 1970-08-04 | Siegfried Sliwinski | Process for the production of methyl phenyl trisiloxanes |
US3792071A (en) * | 1970-12-11 | 1974-02-12 | Wacker Chemie Gmbh | Process for the manufacture of alkoxysilanes and alkoxy-polysiloxanes |
-
1981
- 1981-02-12 US US06/234,027 patent/US4309557A/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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GB787800A (en) * | 1955-10-07 | 1957-12-18 | Midland Silicones Ltd | A novel trisiloxane |
GB808613A (en) * | 1957-01-03 | 1959-02-04 | Midland Silicones Ltd | Trisiloxane |
US2890234A (en) * | 1957-01-03 | 1959-06-09 | Dow Corning | Phenylmethyltrisiloxanes |
US3334318A (en) * | 1964-12-05 | 1967-08-01 | Mitsubishi Electric Corp | Stripline circulator having means causing electrostatic capacitance between adjacent pairs of terminals to be substantially equal to each other |
US3354101A (en) * | 1964-12-29 | 1967-11-21 | Union Carbide Corp | Preparation of organosilicon compounds |
US3523131A (en) * | 1968-10-15 | 1970-08-04 | Siegfried Sliwinski | Process for the production of methyl phenyl trisiloxanes |
US3792071A (en) * | 1970-12-11 | 1974-02-12 | Wacker Chemie Gmbh | Process for the manufacture of alkoxysilanes and alkoxy-polysiloxanes |
Non-Patent Citations (3)
Title |
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Eabor, "Organosilicon Compounds", Butterworth Scientific Pub., London (1960), pp. 300-329. * |
Noll, "Chemistry and Technology of Silicones", Academic Press, N.Y. (1968), pp. 41-49. * |
Sprung et al., J. Am. Chem. Soc., 77, p. 4173 (1955). * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4717773A (en) * | 1985-10-04 | 1988-01-05 | Kenney Malcolm E | Silicate esters and organosilicon compounds |
US4824985A (en) * | 1987-06-11 | 1989-04-25 | Dow Corning Corporation | Novel route to Ca8 Si4 O12 Cl8, alkoxycyclotetrasiloxanes, aryloxycyclotetrasiloxanes, alkylcyclotetrasiloxanes and arylcyclotetrasiloxanes from wollastonite (Ca SiO3) |
US5948539A (en) * | 1996-09-04 | 1999-09-07 | Medtronic, Inc. | Medical electrical lead and reinforced silicone elastomer compositions used therein |
US5952403A (en) * | 1996-09-04 | 1999-09-14 | Medtronic, Inc. | Medical electrical lead and reinforced silicone elastomer compositions used |
US6040369A (en) * | 1996-09-04 | 2000-03-21 | Medtronic, Inc. | Medical electrical lead and reinforced silicone elastomer compositions used therein |
US7329442B2 (en) | 2001-12-21 | 2008-02-12 | Kimberly-Clark Worldwide, Inc. | Elastomeric gloves having improved donnability |
US20030118761A1 (en) * | 2001-12-21 | 2003-06-26 | Kimberly-Clark Worldwide, Inc. | Elastomeric articles having improved chemical resistance |
US20040253459A1 (en) * | 2003-06-11 | 2004-12-16 | Kimberly-Clark Worldwide, Inc. | Composition for forming an elastomeric article |
US20050271842A1 (en) * | 2003-06-11 | 2005-12-08 | Triebes T G | Composition for forming an elastomeric article |
US7052642B2 (en) | 2003-06-11 | 2006-05-30 | Kimberly-Clark Worldwide, Inc. | Composition for forming an elastomeric article |
US20050127578A1 (en) * | 2003-12-11 | 2005-06-16 | Triebes Thomas G. | Method of making fiber reinforced elastomeric articles |
US20050130522A1 (en) * | 2003-12-11 | 2005-06-16 | Kaiyuan Yang | Fiber reinforced elastomeric article |
US20060143767A1 (en) * | 2004-12-14 | 2006-07-06 | Kaiyuan Yang | Breathable protective articles |
CN104017017A (en) * | 2014-06-25 | 2014-09-03 | 四川科立鑫新材料有限公司 | Method for synthesizing phenyl-containing organosilicon monomers |
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